J Mater Sci: Mater Electron (2024) 35:728

CO gas‑sensing properties and DFT investigation

of pure and Co‑modified ­MoO3 nanostructures:
effect of solvent composition, deposition time,
and cobalt concentration
G. M. Ramírez1,2, R. Correa1,2, B. García1, Maria de la Luz Olvera3, C. Vargas2, and
T. V. K. Karthik1,*

1
Escuela de Ingeniería y Ciencias, Departamento de Mecánica y Materiales Avanzados, Tecnológico de Monterrey, Avenida Lago de
Guadalupe KM 3.5, Margarita Maza de Juárez, Lopez Mateos, 52926 Mexico City, Mexico
2
Escuela de Ingeniería y Ciencias, Departamento de Ciencias, Tecnológico de Monterrey, Avenida Lago de Guadalupe, KM 3.5,
Margarita Maza de Juárez, Lopez Mateos, 52926 Mexico City, Mexico
3
SEES, Departamento de Ingeniería Eléctrica, Centro de Investigación y de Estudios Avanzados del Instituto Politécnico Nacional,
CINVESTAV-IPN, 07000 Mexico City, Mexico

Received: 29 November 2023 ABSTRACT

Accepted: 30 March 2024
© The Author(s), under
exclusive licence to Springer
Science+Business Media, LLC,
part of Springer Nature, 2024
In this study, thin films of pure and cobalt-modified molybdenum oxide ­(MoO3)
were deposited using nebulizing spray pyrolysis (NSP). The research delves into
the influence of deposition times (30 and 60 mins), solvents ­(H2O and ­H2O/HCl),
and cobalt modification (3 %wt and 6 %wt) on the structural, morphological, and
electrical properties of the thin films. XRD and FTIR were employed for structural
analysis, while SEM and AFM were used to examine morphology and topogra-
phy. X-ray analysis revealed the predominantly amorphous state of most of the
films, and FTIR allowed visualization of different functional groups of ­MoO3
based on deposition time and dopant concentration. In addition, SEM revealed
an increase in grain size with longer deposition times, and AFM demonstrates
that the cobalt-modified films exhibited higher roughness than pure molybde-
num oxide films. Pure ­MoO3 films using ­H2O as a solvent showed the highest
gas-sensing response to CO at 76%, followed by films modified with 6 wt% Co,
which exhibited a sensing response of 66%. The cobalt-modified films exhibited
a lower sensitivity response than pure films, attributed to the formation of cobalt
oxide. The CO adsorption properties on multiple ­MoO3 structures and ­Co3O4
have been optimized and analyzed using density functional theory (DFT). The
best absorption energy of CO onto the different phases of ­MoO3 and ­Co3O4 has
been reported to contrast it with the experimental results. This study marks the

Address correspondence to E-mail: tvkkarthik@tec.mx

E-mail Addresses: a01707978@tec.mx; a01752813@tec.mx; b.garcia@tec.mx; molvera@cinvestav.mx; claudianvh@tec.mx

https://doi.org/10.1007/s10854-024-12501-y

Vol.:(0123456789)
 728 Page 2 of 14
first report on cobalt-modified molybdenum oxide films, combining theoretical
and practical exploration for CO detection through spray pyrolysis and DFT.
1 Introduction
Currently, the considerable increase in atmospheric
pollution is caused by deleterious gasses, which con-
stitutes a significant challenge for global health [1].
Reports indicate that nearly 3.8 billion individuals
suffer from conditions linked to air pollution, and
approximately 20% of the deaths are attributed to pol-
lution in the domestic environment [2]. CO is posi-
tioned as one of the polluting gasses at higher risk
due to its serious toxicity and colorless, tasteless, and
odorless appearance [3, 4]. The human organism has
an affinity between 250 and 300 times higher for CO
compared to oxygen [4].
The presence of CO in the body causes diseases due
to interference with the blood’s ability to transport
oxygen, as it combines with hemoglobin in the blood
forming carboxyhemoglobin [5]. Likewise, it is noted
that continuous inhalation of CO over a prolonged
period can trigger cardiovascular diseases, increas-
ing the risk of suffering from serious infectious dis-
eases [1]. According to the World Health Organization
(WHO), the time-weighted average exposure limit for
CO is 9 ppm for 8 h and 26 ppm for 1 h [6]. Conse-
quently, the creation of highly sensitive and selective
sensors capable of detecting concentrations below
the threshold limit of CO gas is crucial. This will help
reduce the potential risk to human health and ensure
safety in the public sphere.
Transition metal oxides semiconductors (MOS) have
recently received much attention due to their diverse
structural, morphological, and electrical properties [7]:
Among different MOS, molybdenum oxide ­(MoO3) is
a n-type semiconductor that has an energy bandgap
of ~ 3.20 eV, excellent electron mobility and economi-
cal phase costs, controlled production, non-toxicity,
and multiple valence states [8, 9]. The three different
crystalline structures are thermodynamically stable
orthorhombic ­MoO3 (α-MoO3), metastable monoclinic
­MoO3 (β-MoO3), and hexagonal ­MoO3 (h-MoO3) [10].
The interesting structural and electrical properties of
­MoO3 such as crystalline structure, surface resistance,
surface oxygen vacancies, and physicochemical and
mechanical characteristics, such as refractive index,
energy gap, and hardness out of ß-MoO3 [8] make it
suitable for various technological applications such
J Mater Sci: Mater Electron (2024) 35:728
as catalyzers, in field effect transistors, in gas sensors,
and battery electrodes [11].
Molybdenum oxide has been synthesized using
multiple manufacturing methods categorized into
vapor-, solid-, and liquid-phase deposition techniques.
Due to its popularity in electronic device fabrication,
mostly powder or thin films are required [11, 12]. In
most applications, authors intend to reduce the par-
ticle size making the material more compelling. The
utilization of thin films in gas-sensing applications
offers less sensing material, higher surface area, and
reduction in sensing device size [7]; however, using
powders in gas sensing offers surfaces with very high
porosity and abundant oxygen vacancies [11]. It is
important to choose adequate material depending on
the device’s characteristics. In addition, for visible-
light photocatalysis applications, the thin film has the
advantage of being reusable, as recovering the cata-
lyst after each use requires significantly less effort than
nanoparticles, where catalyst reuse is a laborious pro-
cess [13].
MoO3 thin films have been deposited by various
deposition techniques, such as spray pyrolysis [7–9],
chemical vapor deposition [14, 15], sputtering [16],
gel processing [17], and thermal evaporation [18].
The ultrasonic spray pyrolysis technique has attracted
immense attention to deposit high-quality thin films
because of its one-step deposition. In addition, it is
a simple, fast, and cost-effective (equipment and raw
materials) technique relative to several other bottom-
up synthesis methods [14, 15, 18]. Response and recov-
ery times are the most critical factors for a gas sensor
to be utilized in real-time applications. These prop-
erties can be improved by increasing gas molecules
adsorption and desorption rates by applying ther-
mal energy or temperature. However, increasing the
temperature of a gas sensor results in higher power
consumption. Doping the semiconductor oxide with
metals is known to be a very suitable method for opti-
mizing the parameters of metal oxide gas sensors [7–9,
19]. This is because surface metallic dopants cause (a)
modification of gas molecule adsorption sites or (b)
pinning of the Fermi energy at the surface [20].
For example, Comini et al. [21] studied sol–gel (SG)
and radio-frequency (RF) sputtering techniques for
obtaining ­MoO3 thin films. RF-deposited films have
J Mater Sci: Mater Electron (2024) 35:728
a well-developed nanoparticle microstructure and
a larger surface area than SG-deposited films. The
results have revealed that the ­MoO3 thin films pre-
pared by these techniques are highly sensitive to CO
with very fast response and recovery in the order of a
minute. In addition, Gouider Trabelsi et al. [7] used a
nebulizing spray pyrolysis deposition method to fab-
ricate highly sensitive Co-doped ­MoO3 films to detect
ammonia gas. The authors mentioned that the films
with 3% Co-doped ­MoO3 exhibited faster response
and recovery times than sensors with undoped ­MoO3
film, which is critical for ­MoO3 sensor practical appli-
cations. Furthermore, the ammonia selectivity of the
doped ­MoO3 sensors was found to be very remark-
able. In addition, Yoon Ho Cho et al. [19] achieved
an ultraselective and ultrasensitive trimethylamine
(TMA) sensor using ­MoO3 nanoplates prepared by
ultrasonic spray pyrolysis. The nanoplates showed
an unusually high response to 5 ppm TMA (ratio of
resistance to air and gas = 373.74) at 300 °C with a
detection limit as low as 45 ppb.
In addition, the effect of deposition time [7], the
effect of calcination [10, 19], and different dopants over
the gas-sensing properties have also been studied for
­MoO3 films [7, 22]. However, a study of the effect of
the solvent composition, such as pure ­H2O or ­H2O/
HCl, on the films yet to be reported. We believe that
the change in the solvent composition affects the solu-
bility of the precursor, which in turn changes the pH
of the solution and the thin film growth. Therefore, in
this work, we have deposited molybdenum oxide thin
films by NSP with different Co-dopant concentrations,
solvent compositions, and at different deposition
times. The changes in the structural, topographical,
morphological, and electrical or gas-sensing properties
of ­MoO3 nanostructures were analyzed.
The density functional theory (DFT) calculation is
a technique for analyzing electronic, energetic, and
adsorption properties at the atomic level. The motiva-
tion of this study is to establish a correlation between
the CO adsorption properties on the amorphous (A),
hexagonal (h), and alpha ( 𝛼 ) phases of ­MoO3 and the
experimental results. First principles’ methods based
on DFT have been used to study the sensing mecha-
nism of gas molecules adsorbed on a ­MoO3 surface
[23]. However, the sensing mechanism of a ­Co3O4
structure is considered in this work due to the experi-
mental Co modification of ­MoO3 thin films.
We are the first to report the CO gas-sensing proper-
ties of pure and Co-modified ­MoO3 thin films obtained
Page 3 of 14 728
by NSP. Finally, in this work, a gas-sensing mecha-
nism of pure and Co-modified ­MoO3 sensors for CO
has been reported and discussed in detail.
2 Experimental details
2.1 Film preparation
Thin films of ­MoO3 were deposited on thoroughly
cleaned and dried glass substrates. Two precursor
solutions (Solution A and Solution B) were prepared,
Solution A was made by mixing 0.04 M ammonium
heptamolybdate tetrahydrate ((NH4)6 ­Mo7O24·4H2O)
in deionized water, and Solution B was prepared by
mixing ­H2O and HCl as solvents in a 3:1 ratio, respec-
tively. The total volume of each solution was 100 ml,
and their pH values were 5 and 1 for Solution A and
Solution B, respectively. Appropriate quantities of
cobalt chloride hexahydrate ­(CoCl2·6H2O) were added
to Solution B for modified this film. Two different
weight ratios of [Co]/[Mo]: 3% and 6% were utilized
to observe the effect of Co concentration. All the films
were deposited at 200 °C in a tin bath, with a 1 ml/min
flow rate at 30 and 60 mins utilizing NSP. After the
deposition, films were allowed to cool to room tem-
perature and were calcined at 350 °C for 2 h.
2.2 Characterization techniques
XRD analysis was performed using a PANalytical
diffractometer with CuKα at 20 mA and 40 KV was
carried out to identify the phase compound and the
crystalline structure. Scanning electron microscopy
(SEM JEOL JSM-6360 LV) was used to analyze the
morphology and thickness of the prepared films. The
topography and surface roughness of the synthesized
thin films were examined by atomic force microscopy
(AFM-Park Systems model XE7). The characteristic
functional groups were obtained by Fourier Transform
Infrared Spectroscopy (FTIR-Shimadzu Affinity-1S).
Silver contacts were painted over sensor surfaces for
the gas-sensing measurement and let dry for 20 min at
room temperature. The home-made gas-sensing sys-
tem reported in our previous work [24] was utilized to
obtain all sensors’ sensing response (SR). SR is defined
in Eq. (1), where Ro is the resistance in vacuum and Rg
is the resistance in gas.
 728 Page 4 of 14
RO − Rg
SR = × 100.
Ro
2.3 Density functional theory simulation
Geometry optimization and adsorption energy are
obtained by DFT techniques using the ORCA pro-
gram package (5.0.3) [25]. Geometry optimizations
are treated using Becke’s three-parameter hybrid func-
tional with the Lee–Yang–Parr correlation functional
(B3LYP) [26] in combination with LANL2DZ basis set
on unit cells of multiple ­MoO3 and ­Co3O4 structures.
Cobalt oxide structure is considered instead of pure
Co due to the experimental results obtained (refer to
Sect. 3.2.1: FTIR-XRD analysis). For CO-MoO3/Co3O4
interaction, B3LYP with 6-31G* and LANL2DZ level of
theory was used [27]. The adsorption energies ( Eads )
between CO and ­M oO 3 and ­C o 3O 4 structures are
defined in Eqs. (2) and (3):
( )
Eads = EMoO3 /CO − EMoO3 + ECO , (2)
( )
Eads = ECo3 O4 /CO − ECo3 O4 + ECO ,
where EMoO3 /CO corresponds to the CO adsorption
energy in the different crystal structures of ­MoO3,
ECo3 O4 /CO corresponds to the CO adsorption energy
in ­Co3O4 structure, EMoO3 corresponds to the ­MoO3
adsorption energy, ECo3 O4 corresponds to the ­Co3O4
adsorption energy structure, and then ECO corre-
sponds to the energy of an isolated CO molecule. All
Fig. 1  FTIR spectra of ­MoO3 thin films at 30 and 60 min of deposition a pure with H
J Mater Sci: Mater Electron (2024) 35:728
the mentioned energies in the equation relate to the
(1) equivalently relaxed minimum energy structures.
3 Results and discussion
3.1 E
 ffect of solvent composition based
on deposition time
3.1.1 FTIR‑DRX analysis
Figure 1 shows the FTIR spectra of ­MoO3 thin films
at different deposition times using ­H2O and ­H2O/
HCl (Fig. 1a, b) as solvents. The ­H2O spectra at 30
and 60 min of deposition showed absorption bands
at 761.65 ­cm−1 that are assigned to the Mo–O stretch-
ing vibration and the bands at 885.75 and 908.31 ­cm−1
associated with the Mo=O stretching vibration. On the
other hand, samples with ­H2O/HCl solvents depos-
ited at 30 and 60 min of deposition showed the bands
at 761.65 ­cm−1 associated with the Mo–O stretching
vibration and the bands at 887.25 and 1072.68 ­cm−1 that
are associated with the Mo=O stretching vibration.
From the FTIR spectra of Fig. 1, it can be confirmed
(3) the formation or presence of ­MoO3. Sudesh Kumari
et al. [12] have reported similar characteristic absorp-
tion bands of molybdenum oxide in the wavenumber
range of 400–1200 ­cm−1.
The difference in peak intensity in Fig. 1a may be
attributed to variations in the concentration of the
functional group or changes in the molecular envi-
ronment, an increase in the deposition time resulted
in a red shift in the Mo=O stretching vibration, which
­ 2O as solvent and b pure with ­H2O/HCl as solvents
J Mater Sci: Mater Electron (2024) 35:728
corresponds to a change in the hybridization state or
electron distribution in the molecular bond. In Fig. 1b,
the longer the deposition time, the greater an increase
in transmittance is observed, which resulted due to
increased crystallinity of the material. To confirm the
crystalline structure of the thin films, XRD analysis
of the samples was performed and reported in Fig. 2.
Figure 2 shows the X-ray diffraction analysis of
molybdenum oxide thin films at different deposition
times using ­H2O/HCl as a solvent, revealing to the
naked eye an amorphous or nanostructured nature
due to the presence of a wide hump. Sudesh Kumari
et al. [12] also obtained similar results for ­MoO3 thin
Fig. 2  X-ray diffraction patterns of ­MoO3 at 30 and 60 mins of
deposition with ­H2O/HCl as a solvent
Fig. 3  SEM images and 3D AFM images of pure with ­H2O as solvent (a, e and b, f) and pure with ­H2O/HCl as solvents (c, g and d, h)
­MoO3 thin films deposited at 30 and 60 mins, respectively
Page 5 of 14 728
films of 100, 200, and 300 nm thickness. As mentioned
in the experimental details, the substrates were placed
in a tin bath during the deposition which resulted in
certain diffraction peaks at 2θ = 32° and 67° of this
material.
The peaks at (210) and (320) correspond to the hex-
agonal phase of ­MoO3 according to Zhang et al. [28].
The diffraction peaks coincide with JCPDS card No.
21-0569 (space group P63), indicating that hexagonal
­MoO3 was obtained. According to Caique et al. [29]
and Amira et al. [7], the peak at 2θ = 26.5° corresponds
to the alpha phase of ­MoO3. Furthermore, a 30 min
deposition time led to a (210) peak intensity increase,
indicating an anisotropic growth [29] of the h-MoO3
structure and a higher crystallinity. Therefore, two
phases of hexagonal and alpha ­MoO3 were obtained.
3.1.2 SEM‑AFM analysis
With FTIR, it was possible to verify the presence of
­MoO3, however, to achieve a better understanding
of the effect of deposition time, the morphological
and topographic analysis shown in Fig. 3 was carried
out. In the SEM images (Fig. 3a, b), a smooth surface
with homogeneously distributed nanoparticles and
some agglomerates of micron size of 3.33 and 4.8 µm
respectively can be observed. When adding acid to the
solvent (Fig. 3c, d), two different morphologies were
observed: 1. Microcrystal formation is exhibited due
to the coalescence effect, and 2. Microparticles are uni-
formly distributed on the surface. Authors believe that
the second morphology possesses greater roughness
 728 Page 6 of 14 J Mater Sci: Mater Electron (2024) 35:728

and is favorable for sensing. Figure 3c shows the for-

mation of cubic microcrystals with a size of approxi-
mately 2.5–3 µm and Fig. 3d exhibits dendritic struc-
tures with sizes of 5–7 µm. With the transverse SEM
images (Fig. S1), it can be confirmed that the longer
the deposition time, the thickness increases from 224
nm to 88.4 µm and the particle size because there is a
greater amount of material deposited.
It is important to observe that the addition of HCl
in the solvent resulted in different surface morpholo-
gies. Reduction of pH by addition of HCl reduced the
particle size from 4.8 to 3 µm, which is a general phe-
nomenon reported by several authors [30–33] that at
lower pH, formation of ­H3O+ ions is formed, which
prevents the hydrolysis of ­MoO3 and results in smaller
aggregates. On the other hand, authors believe that
addition of HCl could resulted in different cations Fig. 4  FTIR spectra of ­MoO3 thin films of different deposition
of Mo like ­Mo4+ o ­Mo3+ in the spray solution, which times and different percentages of Co
could have resulted in the formation of microcrystals
observed for samples with HCl as solvent [30]. How-
ever, further studies are necessary to corroborate the
result in detail.
During the AFM measurements (Fig. 3e–h), the
fewer rough areas were analyzed, for equipment
safety reasons. In all the films, a very homogeneous
topography is observed. Roughness was calculated
from the AFM height profile of the 5 × 5 µm scanned
area. The 30 and 60 mins ­H2O solvent films (Fig. 3e, f)
showed very similar roughness values of 4.5 and 4.9
nm, respectively, while the roughness values obtained
for the ­H2O/HCl of 30 and 60 min (Fig. 3g, h) were 8.8
and 15.4 nm, respectively. Likewise, it can be observed
that the longer the deposition time, in both cases,
the thickness of the film increases. These substantial
changes in roughness with changes in thickness values
can be attributed to the reflective process of nuclea- Fig. 5  X-ray diffraction patterns of ­MoO3 thin films of different
tion, coalescence, and continuous film growth [34]. deposition times and different percentages of Co

3.2 Effect of Co modification are characteristic of C–O [36]. It can be confirmed from
the FTIR spectra that Co has formed ­Co3O4 instead
3.2.1 FTIR‑DRX analysis of incorporating it into the ­MoO3 crystal structure.
The time effect in both cases with 3% and 6% of Co
Figure 4 shows the FTIR spectra of ­MoO3 thin films at
produced an increase in transmittance, correspond-
different deposition times and different cobalt percent-
ing to the improved crystallinity of the sample with
ages. The spectra showed absorption bands at 625.29
increased deposition time. Besides that, no significant
and 639.30 ­cm−1, which are the characteristics of Co–O
changes between different Co samples percentages are
[35], and the band at 639.30 ­cm−1 associated with the
observed in spectra.
stretching vibration of Mo–O. The bands at 878.31 and
Figure 5 shows the X-ray diffraction analysis of
904.58 ­cm−1 are associated with the Mo=O stretching
molybdenum oxide thin films at different deposition
vibration and the bands at 1060.42 and 1105.29 ­cm−1
J Mater Sci: Mater Electron (2024) 35:728
times and different percentages of Cobalt, revealing
with the naked eye an amorphous or nanostructured
nature due to the presence of a wide hump.
The peak at 2θ = 19° confirms the formation of
­Co3O4 according to Bachiri et al. [37]. The peaks at 2θ
= 26°, 30°, and 43.5° correspond to the hexagonal phase
of ­MoO3 according to Zhang et al. [28]; the peak at 2θ
= 26° and 39° corresponds to the alpha phase of ­MoO3
according to Caique et al. [29] and Amira et al. [7]; and
the peak at 2θ = 32° refers to tin due to the methodol-
ogy used for the deposition of the films.
Therefore, with this image, it can be seen that two
phases of ­MoO3 were obtained, hexagonal and alpha,
with the hexagonal being the most prominent. Fur-
thermore, the films with the longest deposition time
(60 min) presented a more crystalline structure than
the films with a shorter deposition time.
3.2.2 AFM analysis
During the AFM measurements (Fig. 6a–f), the less
rough areas were analyzed, for equipment safety rea-
sons. A very homogeneous topography is observed in
all the films. Roughness was calculated from the AFM
height profile of the 5 × 5 µm scanned area. The 30 and
60 mins films (Fig. 6a, b) showed roughness values of
8.8 and 15.4 nm, respectively.
The 30- and 60-min films with 3 wt% Co (Fig. 6c,
d) obtained a roughness of 26.9 and 56.6 nm, respec-
tively. Finally, the 30- and 60-min films with 6 wt%
Fig. 6  3D AFM images of pure (a, b), 3 wt% Co-doped, (c, d) and 6 wt% Co-doped, (e, f) ­MoO3 thin films deposited at 30 and 60 mins,
respectively
Page 7 of 14 728
Co (Fig. 6e, f) obtained a roughness of 46.6 and 20.8
nm, respectively. Likewise, it can be observed that the
longer the deposition time, in all cases, the thickness of
the film increases. These substantial changes in rough-
ness with changes in thickness values can be attributed
to the reflective process of nucleation, coalescence, and
continuous film growth [34]. The topography with Co
modification presented greater roughness than the
pure films, which would favor sensing.
3.2.3 SEM analysis
In the SEM images (Fig. 7a–f), a smooth surface with
homogeneously distributed microparticles can be
observed, and they exhibit a type of morphology
with the formation of crystals or microstructures due
to the coalescence effect. Figure 7a shows the forma-
tion of cubic crystals with a size of about 2.5–3 µm,
and Fig. 5b exhibits dendritic structures with sizes of
5–7 µm.
Films with 3% of Co (Fig. 7c, d) show preferen-
tial growth with structures of a length of 5 µm and
particles of less than 1 µm while films with 6% of
Co (Fig. 7e, f) have anisotropic growth with struc-
tures with a length of 3 µm and particles of 1 µm to
2 µm. With the SEM images, it can be confirmed that
the longer the deposition time, the larger the parti-
cle size because there is a greater amount of material
deposited, and agglomeration of this occurs and with
 728 Page 8 of 14
Fig. 7  SEM images of
­MoO3 of pure (a, b), 3 wt%
Co-doped (c, d), and 6 wt%
Co-doped (e, f) ­MoO3 thin
films deposited at 30 and 60
mins, respectively
Co modification a different, rougher morphology is
observed, ideal for sensing.
3.3 Gas sensing
The CO-sensing properties of ­MoO3 thin films were
analyzed at different gas concentrations from 10 to
500 ppm at 150 °C, 200 °C, and 300 °C. In general,
the gas-sensing properties were influenced by sev-
eral parameters such as morphology, oxygen vacan-
cies, surface roughness, and crystalline structure. The
above-mentioned parameters can be optimized by
varying sensor-operating temperature, Co concentra-
tions, deposition time, and the solvent used.
Figures 8 and 9 show the ­S R curves of the sen-
sors to CO at different operation temperatures of all
the sensors obtained in this work. It can be observed
J Mater Sci: Mater Electron (2024) 35:728
from the figures that majorly the responses are lin-
ear with respect to gas concentration. However, it is
important to note that for some samples, a saturation
of response is noticed after 200 ppm (See Fig. 9a). It
is well known that the sensing performance depends
mainly on the surface oxygen vacancies, which acts
as the adsorption sites and further gives the sensing
signal. Essentially, the oxygen-deficient sites, which
favors the gas-sensing mechanisms, are closely tied
to its uniformity in the films [1]. Therefore, as long
as the surface contains abundant surface adsorbed
oxygen, the sensing response shows a linear behav-
ior with respect to gas concentration after which
the response saturates, which is generally termed
as detection limit. Authors believe that the linear
behavior is observed between CO concentration
and S R which is due to an increase in the number
J Mater Sci: Mater Electron (2024) 35:728
Fig. 8  Sensing response of the sensors to CO as a function of gas concentration at different temperatures, pure with H
b) and pure with ­H2O/HCl as solvents (c, d) ­MoO3 thin films deposited at 30 and 60 mins, respectively
of interactions between test gas molecules and the
semiconductor surface.
It is well known that the gas-sensing responses
directly depend on the sensor operation temperature.
At lower temperature (below 100 °C), only physisorp-
tion is observed and no electron interchange occurs
between test gas and sample surface. At tempera-
tures between 100 and 300 °C, the chemisorption of
atmospheric oxygen occurs resulting higher sens-
ing responses. In this work, sensing responses were
observed only at 150 and 200 °C. At higher tempera-
tures (above 200 °C), the sensor surface obtained in
this work undergoes an oxidation process because the
samples are amorphous (refer to Sect. 3.2.1: FTIR-DRX
analysis).
Figure 8a–d shows the response of the sen-
sors prepared with ­H2O and ­H2O/HCl as solvents,
Page 9 of 14 728
­ 2O as solvent (a,
respectively. A slightly higher sensitivity can be
observed for the sensors prepared with ­H 2O. On
the contrary, the characterization by SEM and AFM
demonstrated that the films with ­H2O/HCl exhibit
a relatively homogeneous morphology. Further
experiments are necessary for concluding the higher
responses of sensors with ­H2O as solvent.
Figure 9a–d shows the response of the sensors
with 3 wt% and 6 wt% Co-modified ­MoO3 thin films,
respectively. 6 wt% modified films show a very high
SR, and films deposited for 60 min exhibit a better
structure, and higher SR. Finally, it is also evident
that films deposited for 60 min show higher SR than
films deposited at 30 min, irrespective of solvent and
Co concentration. From XRD and FTIR analysis, it
is confirmed that the films with a deposition time
of 60 min are more crystalline which subsequently
increased the response to CO.
 728 Page 10 of 14
Fig. 9  Sensing response of the sensors to CO as a function of gas concentration at different temperatures, 3 wt% Co-doped, (a, b) and 6
wt% Co-doped (c, d) ­MoO3 thin films deposited at 30 and 60 mins, respectively
As in XRD analysis, it is evident the formation of
cobalt oxide, which is a p-type semiconductor; the
p–n junctions between cobalt oxide and molybdenum
oxide resulted in a decrease in the SR for the modified
thin films.
For comparative purposes, SR obtained for all sen-
sors deposited at 30 and 60 min at 300 °C are plotted in
Fig. 10a and b, respectively. From Fig. 10a, it is evident
that the films with ­H2O/HCl solvent show the highest
response of 76% at 500 ppm; however, it is important
to mention that further repeatability tests are neces-
sary to confirm the SR, 54% of SR was observed for the
one prepared with only ­H2O as solvent. On the other
hand, SR around 67% and 44% was recorded for 6 wt%
and 3 wt% modified thin films, respectively.
From Fig. 10b, it is evident that the films with
­H2O solvent show the highest response of 74% at 500
ppm; however, it is important to mention that further
J Mater Sci: Mater Electron (2024) 35:728
repeatability tests are necessary to confirm the SR, 66%
of SR was observed for the one prepared with only
­H2O/HCl as solvent. On the other hand, SR around
70% and 57% was recorded for 6 wt% and 3 wt% mod-
ified thin films, respectively. The authors believe that
the decrease in the SR for the modified samples is also
due to a slight increase in the particle size observed
from SEM analysis. Tayier Yunusi et. al. [31] also
obtained ethanol gas detection result for ­MoO3 thin
films with a very similar SR of 64.1 and for acetone gas
with a lower SR of 36.7.
3.4 Density functional theory simulation
To identify the absorption behavior of CO gas, the
first-principles calculations based on DFT study
considering different positions configurations of
CO molecules were performed to compare the
J Mater Sci: Mater Electron (2024) 35:728 Page 11 of 14 728

Fig. 10  Sensing response of the sensors to CO as a function of the gas concentration at 350 °C with different percentages of cobalt, sol-
vents, and deposition times (a, b) at 30 and 60 mins, respectively

adsorption energies towards the hexagonal (h), alpha The optimized adsorption models of (h), ( 𝛼 ), (A)
( 𝛼 ), and amorphous (A) ­MoO3 structures. Moreover, and ­C o 3O 4 representative molecules are shown in
adsorption energy from ­Co3O4 was also calculated. Fig. 11. Here, the red, pale blue, pale pink, and gray

Fig. 11  Four optimized complex structures: A-MoO3 (a), α-MoO3 (b), h-MoO3 (c), and ­Co3O4 (d)
 728 Page 12 of 14
balls were O, Mo, Co, and C atoms, respectively. In
Table 1, it lists the specific simulation results of all
adsorption systems. It was reported that the greater
the adsorption energy is, the stronger the adsorption
capacity of the structure for the CO gas molecule is
[22].
The calculation results exhibit that the ­Co3O4 had
the most negative adsorption for carbon monoxide
(− 2.65 eV), given that a ­MoO3 molecule exhibited less
adsorption energy (− 0.82 eV). The greater adsorp-
tion energy ( Eads ) was calculated to be between CO
and h-MoO3 (− 12.86 eV). It is noted that the amor-
phous structure presented the weaker adsorption
for CO, which explains the sensing response value
since the amorphous structure is the highest in films.
However, due to the Co-modified ­MoO3, the ­Co3O4
structure formed, and its adsorption energy, authors
believe that CO firstly interacts with it given that it is
a p-type. Thus, it is suggested that ­Co3O4 tends to fill
its vacancies while interacting with CO molecules,
and once full, the sensing mechanisms begin. This
explains the ­SR decreases when having a doped film
n + p-type rather than having a pure one (n-type).
From analyzing Figs. 10, 11, and Table 1, it can be
discussed that the more crystalline the ­M oO 3 film
is, the greater the absorption energy and sensing
response. As it is shown in Table 1, A-MoO 3 pre-
sents the lowest negative adsorption energy (− 9.60
eV) due to its arbitrary molecules’ position, while
h-MoO 3 the highest. Thus, the S R obtained can be
justified considering that it is shown in XRD spectra
that there is more presence of ­MoO3 amorphous state
than the crystalline ones.
Table 1  Adsorption energies
Structure Eads (eV)
from CO complex systems
MoO3 (A) − 9.60
MoO3 (h) − 14.37
MoO3 (𝛼) − 12.86
Co3O4 − 2.65
Table 2  A comparison of
Synthesis method
­MoO3 based gas sensors
NSP
Grinding + sonication
Spray pyrolysis
Chemical bath deposition
Hydrothermal
J Mater Sci: Mater Electron (2024) 35:728
Even though the samples worked for CO gas sens-
ing, more crystalline samples are expected to show
a better sensing response, considering the adsorption
energies obtained during the simulation, and the nega-
tive values obtained that refer to an oxidation process
that can lead to a more crystalline structure formation
on ­MoO3 films. It must be highlighted that interactions
between CO and Co-modified ­MoO3 films may change
when having a more crystalline structure, having a
direct impact on the sensing response system. Table 2
shows a comparison of results obtained in this work
with previously reported ­MoO3 sensors. To the best of
tour knowledge, we are the first to report ­MoO3 sen-
sors obtained by NSP for detecting CO.
4 Conclusions
In this study, NSP successfully deposited thin films
of pure and cobalt-modified ­M oO 3. The research
focused on systematically examining the impact
of deposition times, solvents, and cobalt modifica-
tion on the structural, morphological, and electrical
properties of thin films. Structural analysis by XRD
revealed the predominantly amorphous state of most
of the films, while FTIR showed different functional
groups depending on the deposition time and cobalt
concentration. Morphological and topographic exam-
inations using SEM and AFM indicated an increase
in grain size with deposition times of 60 min and
greater roughness in films modified with cobalt; spe-
cifically the films with 6%wt Co exhibited the greatest
roughness.
The gas-sensing properties were influenced by sev-
eral parameters such as morphology, oxygen vacan-
cies, surface roughness, and crystal structure. It could
be observed that the detection response of the sensors
decreases as the temperature increases. The authors
believe that the sensors undergo an oxidation process
with an increase in temperature because the samples
are amorphous, the results at 300 °C showed that pure
Gas Response (%) Temp. (°C) Conc. (ppm) References
CO 76 300 500 This work
Alcohol 33 300 100 [38]
TMA 12 30 0.5 [39]
NO2 71.8 200 100 [40]
Acetona 38 260 200 [41]
J Mater Sci: Mater Electron (2024) 35:728 Page 13 of 14 728

­MoO3 films using ­H2O as a solvent exhibited the high- Funding

est SR, followed by the modified films with 6 wt% Co.
Analysis of the cobalt-modified films suggested lower Authors did not receive any special funding from any
sensitivity compared to the pure films, attributed to project. Therefore no funding information is added.
the formation of cobalt oxide rather than forming as
a dopant.
DFT calculations were done to add a better under- Data availability
standing on the interactions between CO and the com-
plex systems of the films, showing a greater adsorp- We state that our manuscript is original and unpub-
tion energy with ­Co3O4 than ­MoO3, explaining the lished, and all data are true in the original manuscript
sensing response decrease. Also, multiple ­MoO3 crys- and is not considered for publication elsewhere. We
talline phases were studied, evidencing a greater CO would be grateful if our paper could be reviewed and
interaction when having a crystalline system. Taking considered for publication in the Journal of Materials
all into consideration, this research provided valuable Science: Materials in Electronics.
information on the potential applications of cobalt-
modified ­MoO3 films and several flaws that need to
be improved in future works in order to lay greater Declarations
studies in gas sensing.
Conflict of interest The authors declare that they
have no known competing financial interests or per-
Acknowledgements sonal relationships that could have appeared to influ-
ence the work reported in this paper.
We thank Javier Ulises Arreola for providing the space
and precursors for chemical synthesis, and Mario
Supplementary Information The online version
Andrei Loperena for providing the space for spray
contains supplementary material available at https://​
pyrolysis. Subsequently, we thank the help provided
doi.​org/​10.​1007/​s10854-​024-​12501-y.
by Dr. Dulce Viridiana Melo for the AFM measure-
ments, we thank Juan Jesús Rocha and Kevin Rueda
for the SEM measurements and the technical assis- References
tance for sensing by Miguel Ángel Luna. Finally, we
thank Tecnológico de Monterrey for the socioeconomic 1. A. Ani, P. Poornesh, A. Antony, S. Chattopadhyay, Sens.
scholarships for our studies. Actuators B 399, 134827 (2024)
2. S.M. Majhi, A. Mirzaei, H.W. Kim, S.S. Kim, T.W. Kim,
Nano Energy 79, 105369 (2021)
Author contributions 3. Z.A. Ansari, S.G. Ansari, T. Ko, J.H. Oh, Sens. Actuators
B 87, 105 (2002)
All authors contributed to the conception and design
4. S. Shrivastava, D. Mahana, S. Nehra, S. Gangwar, S. Singh,
of the study. G. M. Ramírez contributed to the experi-
C.S. Yadav, S.K. Muthusamy, A. Dogra, Sens. Actuators B
mentation, analysis, and first draft of the manuscript.
400, 134882 (2024)
R. Correa contributed to the simulations, analysis,
5. D. Zhang, C. Jiang, J. Liu, Y. Cao, Sens. Actuators B 247,
and first draft of simulations. B. García contributed
875 (2017)
to AFM analysis, English revision, and finalization of
6. S. Ghosh, M. Narjinary, A. Sen, R. Bandyopadhyay, S. Roy,
the manuscript. M. de la L. Olvera contributed to the
Sens. Actuators B 203, 490 (2014)
design of experiments and analysis of the detection
7. A. Ben Gouider Trabelsi, F.H. Alkallas, M. Aslam Man-
results. C. Vargas contributed to the design of experi-
thrammel, M. Shkir, S. AlFaify, Results Phys. 43, 106036
ments and the interpretation of simulation results.
(2022)
T. V. K. Karthik contributed to the overall design of
8. R. Jansi, M.S. Revathy, S. Vinoth, A. Kumar, R.S.R. Isaac,
the research work and analysis and interpretation of
N. Deepa, A.M. Al-Enizi, M. Ubaidullah, B. Pandit, M.
XRD, FTIR, SEM, and finalization of the manuscript.
Shahazad, M. Gupta, Opt. Mater. (Amst.) 145, 114464
All authors read and approved the final manuscript.
(2023)
 728 Page 14 of 14 J Mater Sci: Mater Electron (2024) 35:728

9. V. Ganesh, I.S. Yahia, Opt. Mater. (Amst.) 144, 114480
(2023)
10. S. Kumari, P. Singh, H. Singh, K. Singh, A. Kumar, S.
Kumar, A. Thakur, J. Mater. Sci. 32, 24990–24996 (2021)
11. T.H. Chiang, H.C. Yeh, Materials 6, 4609 (2013)
12. S. Kumari, K. Singh, P. Singh, S. Kumar, A. Thakur,
(123AD).
13. M. Sarma, M. KumariJaiswal, S. Podder, J. Bora, S. Kar-
makar, B. Choudhury, A. RatanPal, Physica B 670, 415354
(2023)
14. A. Abdellaoui, L. Martin, A. Donnadieu, Physica Status
Solidi (a) 109, 455 (1988)
15. T. Ivanova, M. Surtchev, K. Gesheva, Mater. Lett. 53, 250
(2002)
16. S. Uthanna, V. Nirupama, J.F. Pierson, Appl. Surf. Sci. 256,
3133 (2010)
17. M. Dhanasankar, K.K. Purushothaman, G. Muralidharan,
Appl. Surf. Sci. 257, 2074 (2011)
18. B. Han, M. Gao, Y. Wan, Y. Li, W. Song, Z. Ma, Mater. Sci.
Semicond. Process. 75, 166 (2018)
19. Y.H. Cho, Y.N. Ko, Y.C. Kang, I.D. Kim, J.H. Lee, Sens.
Actuators B 195, 189 (2014)
20. A. Galdikas, A. Mironas, A. Šetkus, Sens. Actuators B 26,
29 (1995)
21. E. Comini, G. Faglia, G. Sberveglieri, C. Cantalini, M.
Passacantando, S. Santucci, Y. Li, W. Wlodarski, W. Qu,
Sens. Actuators B 68, 168 (2000)
22. Y. Tutel, M.B. Durukan, S.O. Hacioglu, U.C. Baskose,
L. Toppare, H.E. Unalan, Appl. Mater. Today 35, 101924
(2023)
23. K. Xu, N. Liao, B. Zheng, H. Zhou, Phys. Lett. A 384,
126533 (2020)
24. R. Lozano-Rosas, J.M. Bravo-Arredondo, V.K. Karthik-
Tangirala, M.J. Robles-Águila, Appl. Phys. A 129, 1 (2023)
25. ORCA: An Ab Initio, DFT and Semiempirical Electronic
Structure Package (Version 5.0.3). Max Planck Institute for
Chemical Energy Conversion. (2022).
26. A.D. Becke, Phys. Rev. A (Coll Park) 38, 3098 (1988)
27. A.S. Rad, S.S. Shabestari, S. Mohseni, S.A. Aghouzi, J.
Solid State Chem. 237, 204 (2016)
28. C.C. Zhang, L. Zheng, Z.M. Zhang, R.C. Dai, Z.P. Wang,
J.W. Zhang, Z.J. Ding, Phys. Status Solidi B 248, 1119
(2011)
29. C.D.A. Lima, J.V.B. Moura, G.S. Pinheiro, J.F.D.F. Araujo,
S.B.S. Gusmão, B.C. Viana, P.T.C. Freire, C. Luz-Lima,
Ceram. Int. 47, 27778 (2021)
30. B. Yusuf, M.R. Hashim, M.M. Halim, Results Phys. 45,
106229 (2023)
31. T. Yunusi, C. Yang, W. Cai, F. Xiao, J. Wang, X. Su,
Ceram. Int. 39, 3435 (2013)
32. X. Fu, P. Yang, X. Xiao, D. Zhou, R. Huang, X. Zhang, F.
Cao, J. Xiong, Y. Hu, Y. Tu, Y. Zou, Z. Wang, H. Gu, J.
Alloys Compd. 797, 666 (2019)
33. L. Khandare, S.S. Terdale, D.J. Late, Adv. Device Mater.
2, 15 (2016)
34. I. Dundar, M. Krichevskaya, A. Katerski, I.O. Acik, R. Soc.
Open Sci. 6, 181578 (2019)
35. F. Zhang, C. Yuan, X. Lu, L. Zhang, Q. Che, X. Zhang, J.
Power Sources 203, 250 (2012)
36. A. Stadnik, F.Q. Mariani, F.J. Anaissi, S. Afr. J. Chem. 70,
137 (2017)
37. A. El Bachiri, L. Soussi, O. Karzazi, A. Louardi, A. Rmili,
H. Erguig, B. El Idrissi, Spectrosc. Lett. 52, 66 (2019)
38. F. Ji, X. Ren, X. Zheng, Y. Liu, L. Pang, J. Jiang, S. Liu,
Nanoscale 8, 8696 (2016)
39. R. Pandeeswari, B.G. Jeyaprakash, Biosens. Bioelectron.
53, 182 (2014)
40. A.A. Felix, R.A. Silva, M.O. Orlandi, CrystEngComm 22,
4640 (2020)
41. H. Yan, P. Song, S. Zhang, Z. Yang, Q. Wang, RSC Adv. 5,
72728 (2015)
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